Interconversion of Formic Acid and Carbon Dioxide by Proton-Responsive, Half-Sandwich Cp*IrIII Complexes: A Computational Mechanistic Investigation

ACS Catalysis ◽  
2015 ◽  
Vol 6 (2) ◽  
pp. 600-609 ◽  
Author(s):  
Mehmed Z. Ertem ◽  
Yuichiro Himeda ◽  
Etsuko Fujita ◽  
James T. Muckerman
Keyword(s):  
Carbon Dioxide ◽  
Formic Acid ◽  
Mechanistic Investigation ◽  
Half Sandwich

Photochemical and Electrochemical Reduction of Carbon Dioxide Catalyzed by a Polyoxometalate-Organic Photosensitizer Complex

2018 ◽  
Author(s):  
Chandan Dey ◽  
Ronny Neumann
Keyword(s):  
Carbon Dioxide ◽  
Cyclic Voltammetry ◽  
Formic Acid ◽  
Electrochemical Reduction ◽  
Mass Spectroscopy ◽  
Photochemical Reactions ◽  
Reducing Agent ◽  
Covalent Attachment ◽  
Hybrid Complex ◽  
Open Face

<p>A manganese substituted Anderson type polyoxometalate, [MnMo<sub>6</sub>O<sub>24</sub>]<sup>9-</sup>, tethered with an anthracene photosensitizer was prepared and used as catalyst for CO<sub>2</sub> reduction. The polyoxometalate-photosensitizer hybrid complex, obtained by covalent attachment of the sensitizer to only one face of the planar polyoxometalate, was characterized by NMR, IR and mass spectroscopy. Cyclic voltammetry measurements show a catalytic response for the reduction of carbon dioxide, thereby suggesting catalysis at the manganese site on the open face of the polyoxometalate. Controlled potentiometric electrolysis showed the reduction of CO<sub>2</sub> to CO with a TOF of ~15 sec<sup>-1</sup>. Further photochemical reactions showed that the polyoxometalate-anthracene hybrid complex was active for the reduction of CO<sub>2</sub> to yield formic acid and/or CO in varying amounts dependent on the reducing agent used. Control experiments showed that the attachment of the photosensitizer to [MnMo<sub>6</sub>O<sub>24</sub>]<sup>9-</sup> is necessary for photocatalysis.</p><div><br></div>

Dehydrogenation of Formic Acid by a Ru II Half Sandwich Catalyst

2021 ◽  
Vol 6 (35) ◽  
pp. 9447-9452
Author(s):  
Aditi Vatsa ◽  
Sumanta Kumar Padhi
Keyword(s):  
Formic Acid ◽  
Half Sandwich

THE KINETICS OF THE OXIDATION OF GASEOUS ACETALDEHYDE

1932 ◽  
Vol 7 (2) ◽  
pp. 149-161 ◽  
Author(s):  
W. H. Hatcher ◽  
E. W. R. Steacie ◽  
Frances Howland
Keyword(s):  
Carbon Dioxide ◽  
Formic Acid ◽  
Induction Period ◽  
Reaction Vessel ◽  
Oxidation Products ◽  
Main Reaction ◽  
Chain Mechanism ◽  
Subsequent Reaction ◽  
A Chain ◽  
Kinetics Of

The kinetics of the oxidation of gaseous acetaldehyde have been investigated from 60° to 120 °C. by observing the rate of pressure decrease in a system at constant volume. A considerable induction period exists, during which the main products of the reaction are carbon dioxide, water, and formic acid. The main reaction in the subsequent stages involves the formation of peroxides and their oxidation products. The heat of activation of the reaction is 8700 calories per gram molecule. The indications are that the reactions occurring during the induction period are heterogeneous. The subsequent reaction occurs by a chain mechanism. The chains are initiated at the walls of the reaction vessel, and are also largely broken at the walls.

Simple and recyclable ionic liquid based system for the selective decomposition of formic acid to hydrogen and carbon dioxide

2011 ◽  
Vol 13 (6) ◽  
pp. 1411 ◽  
Author(s):  
M. E. M. Berger ◽  
D. Assenbaum ◽  
N. Taccardi ◽  
E. Spiecker ◽  
P. Wasserscheid
Keyword(s):  
Carbon Dioxide ◽  
Ionic Liquid ◽  
Formic Acid

scholarly journals Harnessing Escherichia coli for bio-based production of formate under pressurized H 2 and CO 2 gases.

2021 ◽  
Author(s):  
Magali Roger ◽  
Thomas C. P. Reed ◽  
Frank Sargent
Keyword(s):  
Escherichia Coli ◽  
Carbon Dioxide ◽  
Formic Acid ◽  
Carbon Capture ◽  
Continuous Production ◽  
Carbon Capture And Storage ◽  
Physiological Role ◽  
Anaerobic Growth ◽  
Formate Hydrogenlyase ◽  
And Storage

Escherichia coli is gram-negative bacterium that is a workhorse for biotechnology. The organism naturally performs a mixed-acid fermentation under anaerobic conditions where it synthesises formate hydrogenlyase (FHL-1). The physiological role of the enzyme is the disproportionation of formate in to H 2 and CO 2 . However, the enzyme has been observed to catalyse hydrogenation of CO 2 given the correct conditions, and so has possibilities in bio-based carbon capture and storage if it can be harnessed as a hydrogen-dependent CO 2 -reductase (HDCR). In this study, an E. coli host strain was engineered for the continuous production of formic acid from H 2 and CO 2 during bacterial growth in a pressurised batch bioreactor. Incorporation of tungsten, in place of molybdenum, in FHL-1 helped to impose a degree of catalytic bias on the enzyme. This work demonstrates that it is possible to couple cell growth to simultaneous, unidirectional formate production from carbon dioxide and develops a process for growth under pressurised gases. IMPORTANCE Greenhouse gas emissions, including waste carbon dioxide, are contributing to global climate change. A basket of solutions is needed to steadily reduce emissions, and one approach is bio-based carbon capture and storage. Here we present out latest work on harnessing a novel biological solution for carbon capture. The Escherichia coli formate hydrogenlyase (FHL-1) was engineered to be constitutively expressed. Anaerobic growth under pressurised H 2 and CO 2 gases was established and aqueous formic acid was produced as a result. Incorporation of tungsten in to the enzyme in place of molybdenum proved useful in poising FHL-1 as a hydrogen-dependent CO 2 reductase (HDCR).

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